Compositions for endodontic procedures

ABSTRACT

An adhesion promoter for endodontic sealant compositions for filling and sealing a root canal.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims the benefit of and priority to U.S.Provisional Patent Application Ser. No. 61/671,251, filed on Jul. 13,2012, which are herein incorporated by reference for all purposes.

FIELD OF THE INVENTION

The present invention is directed to a dental composition, andspecifically to an improved composition for endodontic procedures usefulfor filling root canals.

BACKGROUND OF THE INVENTION

Previous root canals procedures included a step of sealing the rootcanal with a sealant material and then a step of filling the sealed rootcanal with a filling material. Most typical “sealers” are generallyhydrocarbon based amine/epoxy systems, which may result in an unstablesystem when mixed with powder of a filling material such as ground upgutta-percha points.

Gutta-percha is the most widely used obturation material. However,gutta-percha does not create a seal. It is a second composition referredto as a sealer which creates the seal and then the two materials worktogether to prevent bacteria from entering the canal system. Thegutta-percha can be improved by heating it above its melt temperaturethus allowing it to flow. The melted gutta-percha is compacted with aheated a plugger or a solid carrier. The liquid gutta-percha flows intotubules carrying sealer along with it, thus, creating a more completeseal of the root canal system. However, heated gutta-percha has a veryhigh viscosity and tends to be tacky. So, while it flows, it cannotpenetrate all tubules or openings, thus the sealer cannot completelyseal the entire system.

The gutta-percha can be improved by heating it above its melttemperature thus allowing it to flow. The melted gutta-percha iscompacted with a heated a plugger or a solid carrier. The liquidgutta-percha flows into tubules carrying sealer along with it, thus,creating a more complete seal of the root canal system. However, heatedgutta-percha has a very high viscosity and tends to be tacky. So, whileit flows, it cannot penetrate all tubules or openings, thus the sealercannot completely seal the entire system.

Since the sealer will be in the canal system in very thin layers it mustbe very radiopaque to be seen on the x-ray. Therefore, sealers aretypically a reactive composite made up mostly of radiopacifier. If thesealer is to flow to fill the very small gaps to create the seal, thepolymer portion of the composite must be a very low viscosity (lowmolecular weight).

Many sealer formulations have been used over the years, zinc oxideeugenol, epoxy amines and acrylates. All these two part systems areheavily filled liquids which once mixed form a paste and then later setinto a solid. Sealers of this type cannot be used without thegutta-percha since they would be nearly impossible to retreat, have nomethod to compact them into the tubules and are not formulated to beused in thick layers.

Although these traditional gutta-percha sealer compositions aregenerally effective in treating root canals, it would be desirable tohave a gutta-percha/sealer 2 in 1 composition which could fill the canalsystem without the need for heat. Ideally, the 2 in 1 composition wouldhave a lower viscosity and be less tacky than melted gutta-percha. Thisimprovement would increase the penetration of the composition into thecomplex of tubules and tiny openings to more completely seal the entireroot canal system. More particularly, the present invention attempts toovercome these deficiencies by providing stable improved 2-in-1 sealercomposition (e.g., a composite sealant composition) and/or adhesionpromoter with optional cross-linked formulations and methods fortreating root canals using compositions thereof. Desirably, the presentinvention provides such improved obturation compositions having thesedesirable properties as well as other beneficial features andadvantages.

SUMMARY OF THE INVENTION

The present invention seeks to improve upon prior obturation systems andparticularly the filling a tooth root canal.

In one aspect, the present invention contemplates an endodonticcomposite sealant composition for filling and sealing a root canalcomprising: cross-linked-polyisoprene microparticles.

In another aspect, the present invention contemplates an endodonticcomposite sealant composition for filling and sealing a root canalcomprising an adhesion promoter.

In another aspect, the present invention contemplates a method forsealing a root canal with a composite sealant composition comprising thesteps of: providing a mixture including cis-polyisoprene, across-linker, an initiator, a filler, zinc oxide and radiopacifier;curing the mixture to form a cured cross-linked cis-polyisoprenematerial; grinding the cured cross-linked cis-polyisoprene materialcryogenically to form microparticles; providing a first componentmixture including an epoxy based polymerizable compound and at least oneof a radiopacifier, a filler, and the cured cross-linkedcis-polyisoprene microparticles; providing a second component mixtureincluding an amine-based polymerizable compound, a curing agent and atleast one of a radiopacifier, a filler, and the cured cross-linkedcis-polyisoprene microparticles; and filling the root canal with thefirst component mixture and the second component mixture to form a curedcomposite sealant material; wherein the first component mixture, thesecond component mixture, or both include the cured cross-linkedcis-polyisoprene microparticles.

In another aspect, the present invention contemplates An adhesionpromoter comprising the following formula (I): R¹—R²—W—Z—R³—R⁴ (I)wherein

W is

or W is

and Z is

wherein R¹ and R⁴ are independently Hydrogen, NH₂, OH, COOH, SH, anepoxide, a succunic anhydride, a succinimide group, a phosphate, asulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, adiacids, a bisphosphate, or a phosphatidylcholine group; R² and R³ areindependently a C₁₋₁₀ alkyl group, NH₂, OH, COOH, SH, an epoxide, asuccunic anhydride, a succinimide group, a phosphate, a sulfate, asulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, abisphosphate, or a phosphatidylcholine group; R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, and R¹² are independently Hydrogen, a C₁₋₁₀ alkyl group, or aC₁₋₁₀—R¹³ group such that R¹³ is independently NH₂, OH, COOH, SH, anepoxide, a succunic anhydride, a succinimide group, a phosphate, asulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, adiacids, a bisphosphate, or a phosphatidylcholine group, whereasmultiple groups of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ may beidentical or different; and x is an integer from 1 to 1000, multiplegroups of x may be identical or different; y is an integer from 1 to1000, multiple groups of y may be identical or different; and m is aninteger from 1 to 1000, multiple groups of m may be identical ordifferent.

In yet another aspect, any of the aspects of the present invention maybe further characterized by one or any combination of the followingfeatures: the cross-linked-polyisoprene microparticles are synthesizedfrom cis-polyisoprene; further comprising a polymerizable compound, acuring agent, and a filler; a portion of the polymerizable compoundincludes a ring-opening functionality, a reactive-cyclic functionality,a free radical functionality, or any combination thereof; thering-opening functionality is selected from the group consisting of anacid group, an amine group, a thiol group and an alcohol group; thereactive-cyclic functionality is selected from the group consisting ofan epoxy group, an anhydride group, an aziridine group and an oxazolonegroup; the free radical functionality is selected from the groupconsisting of a double bond and a triple bond; the adhesion promoterincludes a dentin binding functionality; the dentin bindingfunctionality includes a negative charge, a positive charge, anamphoteric charge, or a zwitterionic charge; the negative or positivecharge comprises carboxylic acid groups, sulfate groups, amine groups,phosphate groups, quaternary ammonium groups and sulfonate, betaine,phosphatidylcholine groups; the cross-linked polyisoprene microparticlesare less than about 200 um; the cross-linked-cis-polyisoprenemicroparticles range from about 50 to about 180 urn; up to about 50% byweight is the cross-linked cis-polyisoprene powder, wherein thecomposition further comprises: up to about 80 weight % a radiopacifierselected from the group consisting of tungsten, zinc, zinc oxide,tungsten oxide, barium, barium sulfate, bismuth, bismuth oxide, andcalcium tungstate; up to about 10% a curing agent, up to about 40% afiller, wherein the filler is a polymer, silica,cross-linked-cis-polyisoprene microparticles or fumed silica, or anycombination thereof, and up to about 50% an adhesion promoter; thecuring agent includes a catalyst having an amine group; thecross-linked-cis-polyisoprene microparticles comprises fibers,crosslinking agents, initiators, radiopacifiers, cis-polyisoprene,and/or antimicrobial agent; the initiator is selected from the groupconsisting of a free radical initiator or cationic initiator, andplatinum initiator; the adhesion promoter is characterized by thefollowing formula (I): R¹—R²—W—Z—R³—R⁴ (I) wherein

W is

or W is

and Z is

wherein R¹ and R⁴ are independently Hydrogen, NH₂, OH, COOH, SH, anepoxide, a succunic anhydride, a succinimide group, a phosphate, asulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, adiacids, a bisphosphate, or a phosphatidylcholine group; R² and R³ areindependently a C₁₋₁₀ alkyl group, NH₂, OH, COOH, SH, an epoxide, asuccunic anhydride, a succinimide group, a phosphate, a sulfate, asulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, abisphosphate, or a phosphatidylcholine group; R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, and R¹² are independently Hydrogen, a C₁₋₁₀ alkyl group, or aC₁₋₁₀—R¹³ group such that R¹³ is independently NH₂, OH, COOH, SH, anepoxide, a succunic anhydride, a succinimide group, a phosphate, asulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, adiacids, a bisphosphate, or a phosphatidylcholine group, whereasmultiple groups of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ may beidentical or different; and x is an integer from 1 to 1000, multiplegroups of x may be identical or different; y is an integer from 1 to1000, multiple groups of y may be identical or different; and m is aninteger from 1 to 1000, multiple groups of m may be identical ordifferent; wherein i) R¹ and R⁴ are independently an epoxide, a succunicanhydride, or a succinimide group; ii) R¹ and R⁴ are independently NH₂,OH, COOH, or SH group; or iii) at least one of R¹ and R⁴ isindependently a phosphate, a sulfate, a sulfonate, a betaine, acarboxylic acid, an amino acid, a diacids, a bisphosphate, or aphosphatidylcholine group; wherein i) R¹ and R⁴ are independently anepoxide, a succunic anhydride, or a succinimide group; and ii) at leastone of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently theC₁₋₁₀—R¹³ group such that R¹³ is independently the phosphate, thesulfate, the sulfonate, the betaine, the carboxylic acid, the aminoacid, the diacids, the bisphosphate, or the phosphatidylcholine group;wherein: i) R¹ and R⁴ are independently NH₂, OH, COOH, or SH group; andii) at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² isindependently the C₁₋₁₀—R¹³ group such that R¹³ is independently thephosphate, the sulfate, the sulfonate, the betaine, the carboxylic acid,the amino acid, the diacids, the bisphosphate, or thephosphatidylcholine group; wherein: i) at least one of R¹ and R⁴ isindependently a phosphate, a sulfate, a sulfonate, a betaine, acarboxylic acid, art amino acid, a diacids, a bisphosphate, or aphosphatidylcholine group; and ii) at least one of R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, and R¹² is independently the C₁₋₁₀—R¹³ group such that R¹³ isindependently the NH₂, OH, COOH, SH, epoxide, succunic anhydride, orsuccinimide group, whereas NH₂, OH, COOH, or SH group is not presentwhen the epoxide, the succunic anhydride, or the succinimide group ispresent; wherein R⁵, R⁶, R¹¹, and R¹² are independently a C₁₋₁₀ alkylgroup; wherein:

W is

andwherein R¹ and R⁴ are independently NH₂, OH, COOH, SH, an epoxide, asuccunic anhydride, or a succinimide group; R² and R³ are independentlya C₁₋₁₀ alkyl group; and R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² areindependently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹³ group suchthat R¹³ is independently a phosphate, a sulfate, a sulfonate, abetaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, ora phosphatidylcholine group, whereas multiple groups of R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², and R¹³ may be identical or different; wherein NH₂, OH, COOH,or SH is not present when the epoxide, the succunic anhydride, or thesuccinimide group is present; wherein at least one of R⁵, R⁶, R⁷, R⁸,R⁹, R¹⁰, R¹¹, and R¹² includes the C₁₋₁₀—R¹³ group; wherein at least oneof R⁷ and R⁸ includes the C₁₋₁₀—R¹³ group; wherein R⁵, R⁶, R¹¹, and R¹²are independently a C₁₋₁₀ alkyl group; wherein:

W is

andwherein R¹ and R⁴ are independently Hydrogen, a phosphate, a sulfate, asulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, abisphosphate, or a phosphatidylcholine group, provided at least one ofR¹ and R⁴ is not Hydrogen; R² and R³ are independently a C₁₋₁₀ alkylgroup; and R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independentlyHydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹³ group such that R¹³ isindependently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, or asuccinimide group, whereas multiple groups of R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,and R¹³ may be identical or different, provided at least two of R⁵, R⁶,R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² includes the C₁₋₁₀—R¹³ group; wherein NH₂,OH, COOH, or SH is not present when the epoxide, the succunic anhydride,or the succinimide group is present; wherein at least two of R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, and R¹² includes the C₁₋₁₀—R¹³ group; wherein x rangesfrom 1-50, y ranges from 25-250, and m is 1; wherein the adhesionpromoter includes a first component and a second component, a) the firstcomponent is characterized by the following formula (IIa):R¹—R²—W—Z—R³—R⁴ (IIa); wherein R¹ and R⁴ are independently NH₂, OH,COOH, or SH; R² and R³ are independently a C₁₋₁₀ alkyl group;

W is

Z is

R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² are independently Hydrogen, a C₁₋₁₀alkyl group, or a C₁₋₁₀—R¹³ group such that R¹³ is independently aphosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, anamino acid, a diacids, a bisphosphate, or a phosphatidylcholine group,whereas multiple groups of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹³ may beidentical or different; x is an integer from 1 to 1000, multiple groupsof x may be identical or different; y is an integer from 1 to 1000,multiple groups of y may be identical or different; and m is an integerfrom 1 to 10, multiple groups of m may be identical or different; and b)the second component is characterized by the following formula (IIb):R¹³—R¹⁴—W—Z—R¹⁵—R¹⁶ (IIb); wherein R¹³ and R¹⁶ are independently anepoxide, a succunic anhydride, or a succinimide group; R¹⁴ and R¹⁵ areindependently a C₁₋₁₀ alkyl group;

W is

Z is

R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², and R²³ are independently Hydrogen, aC₁₋₁₀ alkyl group, or a C₁₋₁₀—R²⁴ group such that R²⁴ is independently aphosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, anamino acid, a diacids, a bisphosphate, or a phosphatidylcholine group,whereas multiple groups of R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, andR²⁴ may be identical or different; q is an integer from 1 to 1000,multiple groups of q may be identical or different; r is an integer from1 to 1000, multiple groups of r may be identical or different; and s isan integer from 1 to 10, multiple groups of s may be identical ordifferent; wherein i) at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²includes the C₁₋₁₀—R¹³ group; and/or ii) at least one of R¹⁶, R¹⁷, R¹⁸,R¹⁹, R²⁰, R²¹, R²², and R²³ includes the C₁₋₁₀—R²⁴ group; wherein i) atleast one of R⁷ and R⁸ includes the C₁₋₁₀—R¹³ group; and/or ii) at leastone of R¹⁸ and R¹⁹ includes the C₁₋₁₀—R²⁴ group; wherein x ranges from1-50, y ranges from 25-250, and m is 1 and wherein q ranges from 1-50, rranges from 25-250, and s is 1; wherein the adhesion promoter includes afirst component and a second component, a) the first component ischaracterized by the following formula (IIIa): R¹—R²—W—Z—R³—R⁴ (IIIa);wherein R¹ and R⁴ are independently Hydrogen, a phosphate, a sulfate, asulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, abisphosphate, or a phosphatidylcholine group, provided at least one ofR¹ and R⁴ is not Hydrogen; R² and R³ are independently a substituted orunsubstituted C₁₋₁₀ alkyl group;

W is

Z is

R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² are independently Hydrogen, a C₁₋₁₀alkyl group, or a C₁₋₁₀—R¹³ group such that R¹³ is independently NH₂,OH, COOH, SH, whereas multiple groups of R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², andR¹³ may be identical or different; x is an integer from 1 to 1000,multiple groups of x may be identical or different; y is an integer from1 to 1000, multiple groups of y may be identical or different; and m isan integer from 1 to 10, multiple groups of m may be identical ordifferent; and b) the second component is characterized by the followingformula (IIIb): R¹³—R¹⁴—W—Z—R¹⁵—R¹⁶ (IIIb); wherein R¹³ and R¹⁶ areindependently Hydrogen, a phosphate, a sulfate, a sulfonate, a betaine,a carboxylic acid, an amino acid, a diacids, a bisphosphate, or aphosphatidylcholine group, provided at least one of R¹ and R⁴ is notHydrogen; R¹⁴ and R¹⁵ are independently a substituted or unsubstitutedC₁₋₁₀ alkyl group;

W is

Z is

R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², and R²³ are independently Hydrogen, aC₁₋₁₀ alkyl group, or a C₁₋₁₀—R²⁴ group such that R²⁴ is independentlyan epoxide, a succunic anhydride, or a succinimide group, whereasmultiple groups of R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, and R²⁴ maybe identical or different; q is an integer from 1 to 1000, multiplegroups of q may be identical or different; r is an integer from 1 to1000, multiple groups of r may be identical or different; and s is aninteger from 1 to 10, multiple groups of s may be identical ordifferent; wherein i) at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²includes the C₁₋₁₀—R¹³ group; and/or ii) at least one of R¹⁶, R¹⁷, R¹⁸,R¹⁹, R²⁰, R²¹, R²², and R23 includes the C₁₋₁₀—R²⁴ group; wherein xranges from 1-50, y ranges from 25-250, and m is 1; and wherein q rangesfrom 1-50, r ranges from 25-250, and s is 1; wherein adhesion promoteris characterized by the following formula (IV): R¹—W—Z—R² (IV) whereinR¹ and R² are independently a substituted or unsubstituted C₁₋₁₁ alkylgroup;

W is

or W is

and Z is

wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently Hydrogen,a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹¹ group such that R¹¹ is independentlyNH₂, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimidegroup, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylicacid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholinegroup; whereas multiple groups of R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, andR¹¹ may be identical or different; provided that at least one of R³, R⁴R⁵, R⁶, R⁷, and R⁸ includes the C₁₋₁₀—R¹¹ group; x is an integer from 1to 1000, multiple groups of x may be identical or different; y is aninteger from 1 to 1000, multiple groups of y may be identical ordifferent; and m is an integer from 1 to 10, multiple groups of m may beidentical or different; wherein NH₂, OH, COOH, or SH is not present whenthe epoxide, the succunic anhydride, or the succinimide group ispresent; wherein

W is

andwherein R³, R⁴, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ include the C₁₋₁₀ alkyl group;x ranges from 1-50; y ranges from 25-250; and m is 1; wherein theadhesion promoter includes a first component and a second component, a)the first component is characterized by the following formula (IVa):R¹—W—Z—R² (IVa) wherein R¹ and R² are independently a substituted orunsubstituted C₁₋₁₁ alkyl group;

W is

and Z is

wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently Hydrogen,a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹¹ group such that R¹¹ is independentlyNH₂, OH, COOH, or SH; whereas multiple groups of R³, R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, R¹⁰, and R¹¹ may be identical or different; provided that at leastone of R³, R⁴ R⁵, R⁶, R⁷, and R⁸ includes the C₁₋₁₀—R¹¹ group; x is aninteger from 1 to 1000, multiple groups of x may be identical ordifferent; y is an integer from 1 to 1000, multiple groups of y may beidentical or different; and m is an integer from 1 to 10, multiplegroups of m may be identical or different; and b) the second componentis characterized by the following formula (IVb): R¹²—W—Z—R¹³ (IVb)wherein R¹² and R¹³ are independently a substituted or unsubstitutedC₁₋₁₁ alkyl group;

W is

and Z is

wherein R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ are independentlyHydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R²² group such that R²² isindependently an epoxide, a succunic anhydride, or a succinimide group;whereas multiple groups of R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, andR²² may be identical or different; provided that at least one of R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ includes the C₁₋₁₀—R¹¹ group; q is aninteger from 1 to 1000, multiple groups of x may be identical ordifferent; r is an integer from 1 to 1000, multiple groups of y may beidentical or different; and s is an integer from 1 to 10, multiplegroups of m may be identical or different; wherein i) at least one ofR⁵, R⁶, R⁷, and R⁸ includes the C₁₋₁₀—R¹¹ group; and ii) at least one ofR¹⁶, R¹⁷, R¹⁸, and R¹⁹ includes the C₁₋₁₀—R²² group; wherein x rangesfrom 1-50, y ranges from 25-250, and m is 1; and wherein q ranges from1-50, r ranges from 25-250, and s is 1; wherein i) at least one of R⁵,R⁶, R⁷, and R⁸ is independently a C₁₋₁₀—R²³ group such that R²³ is aphosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, anamino acid, a diacids, a bisphosphate, or a phosphatidylcholine group;whereas multiple groups of R⁵, R⁶, R⁷, and R⁸ may be identical ordifferent; and/or ii) at least one of R¹⁶, R¹⁷, R¹⁸, and R¹⁹ isindependently a C₁₋₁₀—R²⁴ group such that R²⁴ is a phosphate, a sulfate,a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, abisphosphate, or a phosphatidylcholine group; whereas multiple groups ofR¹⁶, R¹⁷, R¹⁸, and R¹⁹ may be identical or different; wherein theadhesion promoter is characterized by the following formula (V):R¹—R²—W—R³—R⁴ (V) wherein R¹ and R⁴ are independently Hydrogen, NH₂, OH,COOH, SH, an epoxide, a succunic anhydride, or a succinimide group; R²and R³ are independently a C₁₋₁₀₀₀ alkyl group; and

W is

W is

or W is

wherein R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ areindependently Hydrogen, a C₁₋₁₀ alkyl group, or contain a linking groupbeing linked to a NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, asuccinimide group, a phosphate, a sulfate, a sulfonate, a betaine, acarboxylic acid, an amino acid, a diacids, a bisphosphate, aphosphatidylcholine, a hydrocarbon, or a silicone, the linking groupbeing selected from the group consisting of an acrylate group, a(meth)acrylate group, a siloxy acrylate group, a vinyl group, and anallyl group, whereas at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ R¹¹, R¹²,R¹³, R¹⁴, R¹⁵, and R¹⁶ contains the linking group and whereas multiplegroups of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ maybe identical or different; x is an integer from 1 to 1000, multiplegroups of x may be identical or different; y is an integer from 1 to1000, multiple groups of y may be identical or different; and z is aninteger from 1 to 1000, multiple groups of z may be identical ordifferent; wherein NH₂, OH, COOH, or SH is not present when the epoxide,the succunic anhydride, or the succinimide group is present; wherein atleast one of R¹ and R² is NH₂, OH, COOH, SH, an epoxide, a succunicanhydride, or a succinimide group; wherein at least one of R¹³, R¹⁴,R¹⁵, and R¹⁶ contains the linking group being linked to a NH₂, OH, COOH,SH, an epoxide, a succunic anhydride, or a succinimide group; wherein atleast one of R⁵, R⁶, R⁷, R⁸ R⁹, R¹⁰, R¹¹, and R¹² contains the linkinggroup being linked to a phosphate, a sulfate, a sulfonate, a betaine, acarboxylic acid, an amino acid, a diacids, a bisphosphate, aphosphatidylcholine, a hydrocarbon, or a silicone; wherein the siliconeincludes a Tris(trimethylsiloxy)silyl group; wherein

W is

wherein R⁵, R⁶, R⁷, and R⁸ are independently a C₁₋₁₀ alkyl group orcontain a linking group being linked to a phosphate, a sulfate, asulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, abisphosphate, or a phosphatidylcholine, the linking group being selectedfrom the group consisting of an acrylate group, a (meth)acrylate group,a siloxy acrylate group, a vinyl group, and an allyl group, whereas atleast one of R⁵, R⁶, R⁷, and R⁸ contains the linking group and whereasmultiple groups of R⁵, R⁶, R⁷, and R⁸ may be identical or different; R⁹,R¹⁰, R¹¹, and R¹² are independently a C₁₋₁₀ alkyl group or contain alinking group being linked to a hydrocarbon or a silicone group, thelinking group being selected from the group consisting of an acrylategroup, a (meth)acrylate group, a siloxy acrylate group, a vinyl group,and an allyl group, whereas at least one of R⁹, R¹⁰, R¹¹, and R¹²contains the linking group and whereas multiple groups of R⁹, R¹⁰, R¹¹,and R¹² may be identical or different; R¹³, R¹⁴, R¹⁵, and R¹⁶ areindependently a C₁₋₁₀ alkyl group or contain a linking group beinglinked to a NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, or asuccinimide group, the linking group being selected from the groupconsisting of an acrylate group, a (meth)acrylate group, a siloxyacrylate group, a vinyl group, and an allyl group, whereas at least oneof R¹³, R¹⁴, R¹⁵, and R¹⁶ contains the linking group and whereasmultiple groups of R¹³, R¹⁴, R¹⁵, and R¹⁶ may be identical or different;x is an integer from 1 to 100, multiple groups of x may be identical ordifferent; y is an integer from 1 to 100, multiple groups of y may beidentical or different; and z is an integer from 1 to 100, multiplegroups of z may be identical or different; wherein NH₂, OH, COOH, or SHis not present when the epoxide, the succunic anhydride, or thesuccinimide group is present; wherein the silicone includes aTris(trimethylsiloxy)silyl group; wherein the adhesion promoter includesa first component and a second component, a) the first component ischaracterized by the following formula (VIa): R¹—R²—W—R³—R⁴ (VIa);wherein R¹ and R⁴ are independently Hydrogen, an epoxide, a succunicanhydride, or a succinimide group; R² and R³ are independently a C₁₋₁₀₀₀alkyl group; and

W is

wherein R⁵, R⁶, R⁷, and R⁸ are independently Hydrogen, a C₁₋₁₀ alkylgroup, or contain a linking group being linked to a phosphate, asulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, adiacids, a bisphosphate, a phosphatidylcholine, a hydrocarbon, or asilicone, the linking group being selected from the group consisting ofan acrylate group, a (meth)acrylate group, a siloxy acrylate group, avinyl group, and an allyl group, whereas at least one of R⁵, R⁶, R⁷, andR⁸ contains the linking group and whereas multiple groups of R⁵, R⁶, R⁷,and R⁸ may be identical or different; R⁹, R¹⁰, R¹¹, and R¹² areindependently Hydrogen, a C₁₋₁₀ alkyl group, or contain a linking groupbeing linked to a hydrocarbon or a silicone group, the linking groupbeing selected from the group consisting of an acrylate group, a(meth)acrylate group, a siloxy acrylate group, a vinyl group, and anallyl group, whereas at least one of R⁹, R¹⁰, R¹¹, and R¹² contains thelinking group and whereas multiple groups of R⁹, R¹⁰, R¹¹, and R¹² maybe identical or different; R¹³, R¹⁴, and R¹⁶ are independently Hydrogen,a C₁₋₁₀ alkyl group, or contain a linking group being linked to anepoxide, a succunic anhydride, or a succinimide group, the linking groupbeing selected from the group consisting of an acrylate group, a(meth)acrylate group, a siloxy acrylate group, a vinyl group, and anallyl group, whereas at least one of R¹³, R¹⁴, R¹⁵, and R¹⁶ contains thelinking group and whereas multiple groups of R¹³, R¹⁵, and R¹⁶ may beidentical or different; x is an integer from 1 to 1000, multiple groupsx may be identical or different; and y is an integer from 1 to 1000,multiple groups y may be identical or different; and z is an integerfrom 1 to 1000, multiple groups z may be identical or different; and b)the second component is characterized by the following formula (VIb):R¹⁷—R¹⁸—W—E¹⁹—R²⁰ (VIb); wherein R¹⁷ and R²⁰ are independently Hydrogen,NH₂, OH, COOH, or SH; R¹⁸ and R¹⁹ are independently a C₁₋₁₀₀₀ alkylgroup; and

W is

wherein R²¹, R²², R²³, and R²⁴ are independently Hydrogen, a C₁₋₁₀ alkylgroup, or contain a linking group being linked to a phosphate, asulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, adiacids, a bisphosphate, a phosphatidylcholine, a hydrocarbon, or asilicone, the linking group being selected from the group consisting ofan acrylate group, a (meth)acrylate group, a siloxy acrylate group, avinyl group, and an allyl group, whereas at least one of R²¹, R²², R²³,and R²⁴ contains the linking group and whereas multiple groups of R²¹,R²², R²³, and R²⁴ may be identical or different; R²⁵, R²⁶, R²⁷, and R²⁸are independently Hydrogen, a C₁₋₁₀ alkyl group, or contain a linkinggroup being linked to a hydrocarbon or a silicone group, the linkinggroup being selected from the group consisting of an acrylate group, a(meth)acrylate group, a siloxy acrylate group, a vinyl group, and anallyl group, whereas at least one of R²⁵, R²⁶, R²⁷, and R²⁸ contains thelinking group and whereas multiple groups of R²⁵, R²⁶, R²⁷, and R²⁸ maybe identical or different; R²⁹, R³⁰, R³¹, and R³² are independentlyHydrogen, a C₁₋₁₀ alkyl group, or contain a linking group being linkedto a NH₂, OH, COOH, or SH group, the linking group being selected fromthe group consisting of an acrylate group, a (meth)acrylate group, asiloxy acrylate group, a vinyl group, and an allyl group, whereas atleast one of R²⁹, R³⁰, R³¹, and R³² contains the linking group andwhereas multiple groups of R²⁹, R³⁰, R³¹, and R³² may be identical ordifferent; q is an integer from 1 to 1000, multiple groups of q may beidentical or different; and r is an integer from 1 to 1000, multiplegroups of r may be identical or different; and s is an integer from 1 to1000, multiple groups of s may be identical or different; wherein thesilicone of the first component, the second component, or both includesa Tris(trimethylsiloxy)silyl group; wherein theTris(trimethylsiloxy)silyl group is [tris(trimethylsilyloxy)silyl]propylmethacrylate; wherein the amine-based polymerizable compound is an aminemodified polysiloxane compound; wherein the first component mixture, thesecond component mixture, or both include an adhesion promoter; whereinthe adhesion promoter includes a silicon functionality; wherein theadhesion promoter includes a silicon functionality and an amine or epoxyfunctionality; wherein the first component mixture includes an adhesionpromoter having a silicone functionality and an epoxy functionality;wherein the second component mixture includes an adhesion promoterhaving a silicone functionality and an amine functionality; wherein thefirst component mixture includes an adhesion promoter having a siliconefunctionality, an epoxy functionality, and a dentin bindingfunctionality; wherein the second component mixture includes an adhesionpromoter having a silicone functionality, an amine functionality, and adentin binding functionality; wherein the dentin binding functionalityis selected from the group consisting of a phosphate, a sulfate, asulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, abisphosphate, and a phosphatidylcholine; wherein the composite sealantmaterial has a viscosity over 100,000 cps or putty-like; furthercomprising the step of inserting a gutta-percha point, an obturator, ora cross-linked gutta-percha-point into the root canal; wherein thegutta-percha point or carrier is surface modified; wherein the surfacemodification is corona treatment or plasma treatment; wherein thecross-linked cis-polyisoprene microparticles are not soluble in thecomposite sealant material; use of the endodontic composite sealantcomposition described herein; or any combination thereof.

It should be appreciated that the above referenced aspects and examplesare non-limiting as others exist with the present invention, as shownand described herein. For example, any of the above mentioned aspects orfeatures of the invention may be combined to form other uniqueconfigurations, as described herein, demonstrated in the drawings, orotherwise.

DETAILED DESCRIPTION OF THE INVENTION

Desirably, the composite sealant composition includes a cross-linkablematerial, though not required.

In general, the present invention is directed to an improved highstrength composite sealant composition and processes of forming thecomposition. Advantageously, the composite sealant composition can beemployed to form dental sealants with desirable high strengthcharacteristics. This high strength material enables the preparation ofroot canals and may be useful for improved bonding (higher adhesion) tothe tooth dentin and/or root canal points. Dental materials containingpolymerizable resins and filler particles often are used to prepare theroot canals. Such dental materials can be self (chemically)-curable,heat-curable, light-curable, or dual-curable. The dental materials arecured and hardened by different chemical mechanisms to form strong anddurable materials for various dental applications.

In one aspect, the invention solves the problem of the creation of aseal between the sealer and the gutta-percha AND a seal between thesealer and the dentin to prevent leakage of bacteria into the rootcanal. The invention uses rubber formulations cryogenically ground intoa powder and mixed as a filler in various two part polymer systems. Theground rubber can be blended in either one or both parts of the polymersystem. One or more types of ground rubber can be used. This will createa fluid(s) with a paste like viscosity.

The technology to make this work may not be the grinding or thedispersion into the polymer system. It is believed that the formulationof the ground rubber in relation to the polymer system provides the oneof the advantages of this invention.

In another aspect the invention solves the problem of the creation of aseal between the obturation material and the dentine to prevent leakageof bacteria into the root canal. The invention is two ideal molecularadditives which have been designed to bond to collagen ANDhydroxyapatite.

Dentin is composed of a collagen (hydrocarbon polymer) matrix holdingtogether crystalline hydroxyapatite (CaP). The dentin binding moleculesare designed to include three subcomponents in a tri block construction.For example, in a first portion, Block A, may be composed of phosphategroup, in a second portion, Block B, may be composed of trismethacrylate and in a third portion, Block C, may be either a reactivegroup such as an amino methacrylate or a glycidal methacrylate. Block Ais designed to bond to the hydroxyapatite. Block B is designed to be acompatibilizer. Block C is designed to cross link into the networkduring setting (amino/epoxy reaction). The molecular additives aredispersed into two dimethylsiloxanes; an amino functionalized and anepoxy functionalized (see the attached document for more detail).

Polymerizable Materials

The polymerizable material (e.g., a composite sealant composition)typically includes at least one polymerizable component and optionallywithout limitation, one or more of at least one filler (e.g., glassparticles), an adhesion promoter, an initiator, a catalyst, anaccelerator, an inhibitor, surfactant, additive, or combinations thereofor others.

Polymerizable Compounds

Turning now in greater detail to the individual components of theoverall composition. The composite sealant composition herein mayinclude at least one polymerizable material. Desirably, the compositesealant composition may include a first polymerizable material having atleast one of a cyclic compound that is capable of undergoing a ringopening reaction (e.g., a succunic anhydride, a succinimide group, anepoxide, or otherwise) a ring opening nucleophile (e.g., OH, COOH, SH,an amine resin (e.g., NH₂), or otherwise), urethane di-(meth)acrylate,multi(meth)acrylate derivatives of isocyanatomethyl cyclohexane, apolymerizable polysiloxane compound (e.g., an epoxy functionalizedsiloxane, an amino functionalized siloxane, or otherwise), or anycombination thereof.

The first polymerizable material may typically be present in an amountof at least about 1%, preferably at least about 5%, and more preferableat least about 10% by wt the composite sealant composition. Furthermore,it is appreciated that the first polymerizable material may typically bepresent in an amount of less than about 99%, preferably less than about75% and preferably less than about 50% by wt the overall compositesealant composition. For example, the first polymerizable material maytypically be present in an amount ranging from about 1% to about 99%,preferably from about 5% to about 75%, and more preferably from about10% to about 50% by wt the overall composite sealant composition. In onespecific embodiment, the first polymerizable material is thepolymerizable polysiloxane compound.

Examples of polymerizable polysiloxane compounds (e.g.,polydimethylsiloxane copolymers) that may be used in the composition ofthis invention, include, but are not limited to, cyclic compounds thatare capable of undergoing a ring opening reaction such as epoxy modifiedpolysiloxane compounds (e.g., difunctional and multifunctional epoxysilicones) and ring opening nucleophiles such as amine modifiedpolysiloxane compounds (e.g., aminoalkyl functional silicones). Onepreferred epoxy modified polysiloxane is sold under the Tradename EMS622 and is commercially available from Gelest, Inc. One preferred aminemodified polysiloxane is sold under the Tradename AMS 162 and iscommercially available from Gelest, Inc.

The first polymerizable material may include a first component (e.g., acyclic compound that is capable of undergoing a ring opening reaction)and a second component (e.g., ring opening nucleophile) capable ofpolymerization. For example, the polysiloxane compound may include afirst polysiloxane component having an epoxy modified polysiloxane or asecond polysiloxane component having an amine modified polysiloxane. Theepoxy modified polysiloxane may be present in an amount of at leastabout 1%, preferably at least about 3%, and more preferable at leastabout 5% by wt the overall composite sealant composition. Furthermore,the epoxy modified polysiloxane may be present in an amount of less thanabout 50%, preferably less than about 40% and preferably less than about25% by wt the overall composite sealant composition. For example, theepoxy modified polysiloxane may be present in an amount ranging fromabout 1% to about 50%, preferably from about 3% to about 40%, and morepreferably from about 5% to about 25% by wt the overall compositesealant composition. An example of the first polysiloxane componenthaving the epoxy modified polysiloxane may be present as formula (I).

Alternatively or in addition to the first polysiloxane component havingan epoxy modified polysiloxane, the polysiloxane component may include asecond polysiloxane component having an amine modified polysiloxane. Theamine modified polysiloxane may be present in an amount of at leastabout 1%, preferably at least about 3%, and more preferable at leastabout 5% by wt the overall composite sealant composition. Furthermore,the amine modified polysiloxane may be present in an amount of less thanabout 50%, preferably less than about 40% and preferably less than about25% by wt the overall composite sealant composition. For example, theamine modified polysiloxane may be present in an amount ranging fromabout 1% to about 50%, preferably from about 3% to about 40%, and morepreferably from about 5% to about 25% by wt the overall compositesealant composition.

An example of the second polysiloxane component having the aminemodified polysiloxane may be present as formula (II).

Curing Agent

The composite sealant composition herein may include at least oneinitiating component (e.g., catalyst) to effectuate curing of thematerial. The initiating component may be present in an amount of atleast about 0.0005%, preferably at least about 0.005%, and morepreferably at least about 0.05% by wt the overall composite sealantcomposition. The overall composite sealant composition may include lessthan about 3.0%, preferably less than about 1.5%, and more preferablyless than about 1% wt of the initiating component. For example, theinitiating component may be present in a range of about 0.0005% to about3%, preferably from about 0.005% to about 1.5%, and more preferably fromabout 0.05% to about 1% wt of the overall composite sealant composition.

One preferred initiating component includes an alkanol amine. Examplesof suitable alkanol amines include, but are not limited to ethanolamine,2-amino-1-butanol, 4-amino-1-butanol, 2-aminoethanthiol,2-amino-1-hexanol, 2-amino-3-methyl-1-butanol,2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol,5-amino-1-pentanol, 2-(methylamino) ethanol, 2-(propylamino)ethanol,tris(hydroxymethyl)aminomethane, 2-amino-1-propanol, 2-amino-1-pentanol,ethanolamine, 2-hydroxyethylhydoradine, 3-amino-1-propanol,DL-2-amino-1-propanol, DL-1-amino-2-propanol, DL-2-amino-1-pentanol,DL-2-Amino-1-hexanol, 6-amino-1-hexanol, 2-(2-aminoethoxy) ethanol, orotherwise and combinations thereof. Other catalysts are appreciated suchas salts (e.g., platinum, palladium, or otherwise).

As shown in Table 1, an example of acceleration effects for curingvarious composite sealant compositions of the two-component systems withdifferent catalysts:

TABLE 1 I.D. 712A11 712B11 712C11 712D11 712 E11 712U11 AMS 162 50.3%49.5% 49.3% 49.4% 49.0% 85.8% EMS 622 49.7% 49.5% 49.7% 49.5% 50.0%14.2% 2-amino-3methyl-butanol 0.0% 1.0% 0.0% 0.0% 0.0% 0.0%dl-2-amino-1-pentanol 0.0% 0.0% 1.0% 0.0% 0.0% 0.0% dl-2-amino-1-hexanol0.0% 0.0% 0.0% 1.0% 0.0% 0.0% 6-amino-1-hexanol 0.0% 0.0% 0.0% 0.0% 1.0%0.0% Total Mass (g) 10.1 10.1 10.1 10.1 10.3 10.0 Time after mixing tofull 5 3 3 3 5 Not Set, >15 cure (days)

Filler

The composite sealant compositions may include one or more fillers.Fillers having Radiopacity useful in accordance with the invention,without limitation, include inorganic fillers such as Ag, TiO₂, La₂O₃,ZrO₂, BaSO₄, CaWO₄, BaWO₄, Fe₂O₃ and Bi₂O₃, CeO₂, ZrO₂, MgO, lanthanidesalts, polymer granulates, barium or strontium-containing glass. Theglass may contain fluoride for fluoride release in viva. When included,the radiopacifier may be present in an amount of at least about 20%,preferably at least about 30%, and more preferable at least about 40% bywt the overall composite sealant composition. Furthermore, theradiopacifier may be present in an amount of less than about 80%,preferably less than about 70% and preferably less than about 60% by wtthe overall composite sealant composition. For example, theradiopacifier may be present in an amount ranging from about 20% toabout 80%, preferably from about 30% to about 70%, and more preferablyfrom about 40% to about 60% by wt the overall composite sealantcomposition.

Other fillers that may be employed include, but are not limited tosilicas, aluminas, magnesias, titanias, inorganic salts, metallicoxides, (e.g., zinc oxides, calcium hydroxide, or otherwise) andglasses. In one desired embodiment, precipitated silica (e.g., Hi-Sil233) may be included as a filler. In another desired embodiment, fumedsilica (e.g., Aerosil 200) may be included as a filler. The fillermaterial may be present in an amount of at least about 0.1%, preferablyat least about 1%, and more preferably at least about 5% by wt theoverall composite sealant composition. Furthermore, the filler materialmay be present in an amount of Less than about 25%, preferably less thanabout 20% and more preferably less than about 15% by wt the overallcomposite sealant composition. For example, the filler material may bepresent in an amount ranging from about 0.1% to about 25%, preferablyfrom about 1% to about 20%, and more preferably from about 5% to about15% by wt the overall composite sealant composition.

In a preferred embodiment, the composite sealant composition may furtherinclude a cross-linked material (e.g., cross-linked rubber such aspolyisoprene or otherwise). A desirable example of a cross-linkedmaterial may include a cross-linked cis-polyisoprene-based material suchas a cis-1,4-polyisoprene-based material. As shown in Tables 2 and 3,the cross-linked material may include the following compositions asdescribed in U.S. Ser. No 13/045744, filed Mar. 11, 2011, which isherein incorporated by reference for all purposes:

TABLE 2 Component Weight % 1-4, Polyisoprene   10 to 40 Curing Agent 0.1 to 30 Curing Co agent 0.01 to 30 Zinc Oxide   0 to 80 Radiopacifier  0 to 40 Reinforcing Fillers   0 to 50 Carbon Nanotubes   0 to 50Fibers   0 to 50 Colorant   0 to 10

TABLE 3 Component Weight % Cross-Linkable Material  10 to 40 Rubber  0.5to 15 Curing Agent  0.1 to 30 Curing Co agent 0.01 to 15 Antimicrobial0.01 to 50 Radiopacifier  5.0 to 60 Reinforcing Fillers  0.5 to 30Fibers  0.5 to 30 Colorant 0.01 to 25 Anti Oxidant   0 to 10 ProcessingAid   0 to 10

The cross-linked material may be present in an amount of at least about3%, preferably at least about 5%, and more preferably at least about 10%by wt the overall composite sealant composition. Furthermore, thecross-linked material may be present in an amount of less than about50%, preferably less than about 40% and more preferably less than about30% by wt the overall composite sealant composition. For example, thecross-linked material may be present in an amount ranging from about 3%to about 50%, preferably from about 5% to about 40%, and more preferablyfrom about 10% to about 30% by wt the overall composite sealantcomposition.

Desirably, the cross-linked material may be provided as a powder (e.g.,from a grinding or chopping process of the cross-linked material). Thecross-linked material may include a particle size of at least about 5,preferably at least about 10 and more preferably at least about 25microns. Furthermore, the cross-linked material may include a particlesize of less than about 500, preferably less than about 400, and morepreferably less than about 300 microns. For example, the cross-linkedmaterial may include a particle size ranging from about 5 to about 500,preferably from about 10 to about 300, and more preferably from about 25to about 150 microns (e.g., from about 50 microns to about 100 micronsor from about 125 microns to about 200 microns).

As shown in Table 4, one specific example of the two component compositesealant composition containing a cross-linked material:

TABLE 4 Component A Weight % Component B Weight % Reactive-cyclic-based5.0 to 50 Ring-opening-based  5.0 to 50 Polymerizable PolymerizableCompound Compound Catalyst 0 Catalyst 0.001 to 5.0 Radiopacifier  20 to80 Radiopacifier   20 to 80 Reinforcing Fillers 0.1 to 25 ReinforcingFillers  0.1 to 25 Cross-linked Rubber 0.1 to 50 Cross-linked Rubber 0.1 to 50

Desirably, the cyclic-based polymerizable compound includes epoxyfunctionality, while the ring-opening-based polymerizable compoundincludes amine functionality, though not required.

The composite sealant composition may further include additives,pharmaceutical active ingredients, dyes or pigments (e.g., iron oxides)waxes, oils (e.g., silicone oil and paraffin oil), surfactants, fattyacids (e.g., stearic acid), anti-oxidants, preservatives (e.g.,nanosilver), or mixtures thereof.

Adhesion Promoter

The composite sealant composition may further include at least oneadhesion promoter. In one aspect, the adhesion promoter (e.g., secondpolymerizable material) may be present in addition to the polymerizablecompound (e.g., second polymerizable material). In another aspect theadhesion promoter may be the polymerizable compound.

Without intending to be bound by theory, it is believed that theadhesion promoter herein makes advantageous employment of a particularmolecular structure by which at least a portion of the molecule mayinclude cyclic compounds that are capable of undergoing a ring openingreaction functionality (e.g., epoxy group, a succunic anhydride group, asuccinimide group, or otherwise) and/or ring opening nucleophilefunctionality (e.g., OH, COOH, SH amine group, such as diepoxide ordiamine group, or otherwise), which is capable of cross-linking thecomposite sealant composition. The adhesion promoter molecular structuremay include hydrophobic functionality such as a hydrocarbon, a silicone(e.g., it is silanated such as SiO, SiO₂, SiH₄, or SiC), or otherwise,which is capable of being a thickener and/or may be provided as adispersion carrier for the cross-linked material discussed herein. Inone specific embodiment, the silicone functionality includes aTris(trimethylsiloxy)silyl group such as[tris(trimethylsilyloxy)silyl]propyl methacrylate). Furthermore, theadhesion promoter molecular structure may include a dentin bindingfunctionality, such as an phosphate, sulfate, sulfonate, betaine,carboxylic acids, amino acid, diacids, bisphosphate, orphosphatidylcholine functionality, which is capable of improving thelinkage with the tooth dentin such as through the molecular network ofthe composite sealant composition.

The adhesion promoter may be a one component material or a two componentmaterial. Examples of the adhesion promoter include but are not limitedto:

wherein

R¹ is independently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride,or a succinimide group, whereas R¹ may be identical or different,(preferably R¹ is a ring opening nucleophile such as NH₂, OH, COOH, SHor otherwise);

x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x maybe identical or different; and

y is an integer from 1 to 1000, multiple groups of y may be identical ordifferent.

wherein

R² is independently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride,or a succinimide group, whereas multiple groups of R² may be identicalor different, (preferably R² is a ring opening nucleophile such as NH₂,OH, COOH, SH or otherwise);

x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x maybe identical or different;

y is an integer from 1 to 10, multiple groups of y may be identical ordifferent;

A is an integer from 1 to 1000 (e.g., 1 to 100, preferably 1 to 10),multiple groups of A may be identical or different; and

B is an integer from 0 to 1000 (e.g., 1 to 100, preferably 45 to 65),multiple groups of B may be identical or different.

wherein

R³ is independently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride,or a succinimide group, whereas R³ may be identical or different,(preferably R³ is a cyclic compound that may undergo ring polymerizationsuch as an epoxide, a succunic anhydride, a succinimide group, orotherwise);

x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x maybe identical or different; and

y is an integer from 1 to 1000, multiple groups of y may be identical ordifferent.

wherein

R⁴ is independently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride,or a succinimide group, whereas multiple groups of R⁴ may be identicalor different, (preferably R⁴ is a cyclic compound that may undergo ringpolymerization such as an epoxide, a succunic anhydride, a succinimidegroup, or otherwise);

x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x maybe identical or different;

y is an integer from 1 to 10, multiple groups of y may be identical ordifferent;

A is an integer from 1 to 1000, multiple groups of A may be identical ordifferent; and

B is an integer from 0 to 1000 (e.g., 1 to 1000), multiple groups of Bmay be identical or different.

wherein

R⁵ is independently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride,or a succinimide group, whereas multiple groups of R⁵ may be identicalor different;

R⁶ is independently a phosphate, a sulfate, a sulfonate, a betaine, acarboxylic acid, an amino acid, a diacids, a bisphosphate, or aphosphatidylcholine group, whereas multiple groups of R⁶ may beidentical or different;

x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x maybe identical or different;

y is an integer from 1 to 10, multiple groups of y may be identical ordifferent;

A is an integer from 1 to 1000, multiple groups of A may be identical ordifferent; and

B is an integer from 0 to 1000 (e.g., 1 to 1000), multiple groups of Bmay be identical or different; and

wherein R⁵ and R⁶ can change positions.

The adhesion promoter may be a one component material or a two componentmaterial. Examples of the adhesion promoter include but are not limitedto:

wherein

R⁹ is independently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride,or a succinimide group, whereas multiple groups of R⁹ may be identicalor different;

R¹⁰ is independently a phosphate, a sulfate, a sulfonate, a betaine, acarboxylic acid, an amino acid, a diacids, a bisphosphate, or aphosphatidylcholine group, whereas multiple groups of R¹⁰ may beidentical or different;

x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x maybe identical or different;

y is an integer from 1 to 10, multiple groups of y may be identical ordifferent;

z is an integer from 1 to 10, multiple groups of z may be identical ordifferent;

A is an integer from 1 to 1000, multiple groups of A may be identical ordifferent; and

B is an integer from 1 to 1000, multiple groups of B may be identical ordifferent; and

C is an integer from 0 to 1000 (e.g., 1 to 1000), multiple groups of Cmay be identical or different; and

wherein R⁹ and R¹⁰ can change positions.

In a desired embodiment, each functional portion is present therebyforming a ter-polymer adhesion promoter.

wherein

R¹³ is independently a phosphate, a sulfate, a sulfonate, a betaine, acarboxylic acid, an amino acid, a diacids, a bisphosphate, or aphosphatidylcholine group, whereas multiple groups of R¹³ may beidentical or different;

R¹⁴ is independently a hydrophobic group such as a hydrocarbon, asilicone (e.g., it is silanated), or otherwise, (preferably the siliconeincludes a Tris(trimethylsiloxy)silyl group such as[tris(trimethylsilyloxy)silyl]propyl methacrylate), whereas multiplegroups of R¹⁴ may be identical or different;

R¹⁵ is independently NH₂, OH, COOH, SH, an epoxide, a succunicanhydride, or a succinimide group, whereas multiple groups of R¹⁵ may beidentical or different;

n is an integer from 1 to 1000, multiple groups of x may be identical ordifferent;

m is an integer from 0 to 1000 (e.g., 1 to 1000), multiple groups of ymay be identical or different;

p is an integer from 1 to 1000, multiple groups of z may be identical ordifferent; and

wherein R¹³, R¹⁴, and R¹⁵ can change positions.

It is appreciated that a two component adhesion promoter may include afirst component of the formula i)-vii) having a cyclic compound that mayundergo ring polymerization such as an epoxide, a succunic anhydride, asuccinimide group, or otherwise and a second component of the formulai)-vii) having a ring opening nucleophile such as NH₂, OH, COOH, SH orotherwise. When included, polymerization may occur by mixing the firstand second components to form the adhesion promoter.

The adhesion promoter may be synthesized by various processes.Desirably, the ter-polymer adhesion promoter may be formed by RAFTpolymerization to form a two component system. For example, the firstcomponent (having a cyclic compound that may undergo ringpolymerization) may be formed by the following RAFT polymerization:

The second component (having a ring opening nucleophile) may be formedby the following RAFT polymerization:

These specific examples i)-vii) of possible adhesion promoters shouldnot be construed as limiting examples.

In a composite sealant composition that includes at least onepolymerizable compound and at least one adhesion promoter (Examples fromTables 4-7), the adhesion promoter may be present in an amount of atleast about 3%, preferably at least about 5%, and more preferably atleast about 10% by wt the overall composite sealant composition.Furthermore, the adhesion promoter may be present in an amount of lessthan about 50%, preferably less than about 40% and more preferably lessthan about 30% by wt the overall composite sealant composition. Forexample, the adhesion promoter may be present in an amount ranging fromabout 3% to about 50%, preferably from about 5% to about 40%, and morepreferably from about 10% to about 30% by wt the overall compositesealant composition.

TABLE 4 Component A Weight % Component B Weight % Reactive-Cyclic-based5.0 to 25 Ring-opening-based 5.0 to 25 Polymerizable PolymerizableCompound Compound Catalyst 0 Catalyst 0.001 to 5.0  Radiopacifier  20 to80 Radiopacifier 20 to 80 Reinforcing Fillers 0.1 to 25 ReinforcingFillers 0.1 to 25 Cross-linked Rubber 0.1 to 50 Cross-linked Rubber 0.1to 50 Reactive-Cyclic-based 5.0 to 25 Ring-opening-based 5.0 to 25Adhesion Promoter Adhesion Promoter

TABLE 5 Component A Weight % Component B Weight % Reactive-Cyclic-based5.0 to 50 Ring-opening-based 0 Polymerizable Polymerizable CompoundCompound Catalyst 0 Catalyst 0.001 to 5.0  Radiopacifier  20 to 80Radiopacifier 20 to 80 Reinforcing Fillers 0.1 to 25 Reinforcing Fillers0.1 to 25 Cross-linked Rubber 0.1 to 50 Cross-linked Rubber 0.1 to 50Reactive-Cyclic-based 0 Ring-opening-based 5.0 to 50 Adhesion PromoterAdhesion Promoter

TABLE 6 Component A Weight % Component B Weight % Reactive-Cyclic-based0 Ring-opening-based 5.0 to 50 Polymerizable Polymerizable CompoundCompound Catalyst 0 Catalyst 0.001 to 5.0  Radiopacifier  20 to 80Radiopacifier 20 to 80 Reinforcing Fillers 0.1 to 25 Reinforcing Fillers0.1 to 25 Cross-linked Rubber 0.1 to 50 Cross-linked Rubber 0.1 to 50Reactive-Cyclic-based 5.0 to 50 Ring-opening-based 0 Adhesion PromoterAdhesion Promoter

Desirably, the cyclic-based polymerizable compound and the cyclic-basedadhesion promoter include epoxy functionality, while the ringopening-based polymerizable compound and the ring opening-based adhesionpromoter include amine functionality, though not required. It isappreciated that in a composite sealant composition that includes anadhesion promoter as the polymerizable compound (Example of Table 7),the adhesion promoter may in an amount of at least about 1%, preferablyat least about 5%, and more preferably at least about 10% by wt theoverall composite sealant composition. Furthermore, it is appreciatedthat the adhesion promoter may be present in an amount of less thanabout 90%, preferably less than about 70% and preferably less than about50% by wt the overall composite sealant composition. For example, theadhesion promoter may be present in an amount ranging from about 1% toabout 90%, preferably from about 5% to about 70%, and more preferablyfrom about 10% to about 50% by wt the overall composite sealantcomposition.

TABLE 7 Component A Weight % Component B Weight % Reactive-Cyclic-based5.0 to 50 Ring-opening-based  5.0 to 50 Adhesion Promoter AdhesionPromoter Catalyst 0 Catalyst 0.001 to 5.0 Radiopacifier  20 to 80Radiopacifier   20 to 80 Reinforcing Fillers 0.1 to 25 ReinforcingFillers  0.1 to 25 Cross-linked Rubber 0.1 to 50 Cross-linked Rubber 0.1 to 50

Desirably, the cyclic-based adhesion promoter includes epoxyfunctionality, while the ring opening-based adhesion promoter includesamine functionality, though not required.

In one specific two-component example, the product may comprise of aputty formulation, which includes ground cross-linked material (e.g.,ground cross-lined endodontic carriers), silica, polymer, catalyst andbismuth oxide. The formulation mixes into a firm putty which can bedelivered with an amalgum delivery device or with pluggers andspreaders. It has the consistency of a putty and can be rolled into anydesired shaped prior to placing into the canal. Once the canal isfilled, a gutta-percha point or a cross-linked endodontic carrier can beinserted into the canal to facilitate a 3-d fill and prevent leakage outthe apex.

In another specific example, the composite sealant composition maycomprise of an injectable formulation which includes ground cross-linkedmaterial, silica, polymer, catalyst, and bismuth oxide. The formulationmixes in a static mixer connected on the end of a dual syringe. Thematerial is directly injected into the canal. Once the canal is filled,a cross-linked endodontic carrier or gutta-percha-point can be insertedinto the canal to facilitate a 3-d fill and prevent leakage out theapex.

It is appreciated that the gutta-percha point/cross-linked carrierchoice can left up to the clinician (they are interchangeable).

It is further appreciated that in the composite sealant compositionsystems, different types can be used. The sealant material according tothe invention can be present as single-component systems or asmulti-component systems, preferably as two-component systems, as afunction of the polymer system, in each instance. The curable polymersystems and their additional components, such as catalysts and/orinitiators, are known to a person skilled in the art as such.

Preferably, one-component dental sealant materials are used that arecured by means of UV radiation and/or heat. Aside from the curablepolymer system as well as the surfactant mixture used according to theinvention, photoinitiators are usually contained in them

It will be further appreciated that functions or structures of aplurality of components or steps may be combined into a single componentor step, or the functions or structures of one-step or component may besplit among plural steps or components. The present inventioncontemplates all of these combinations. Unless stated otherwise,dimensions and geometries of the various structures depicted herein arenot intended to be restrictive of the invention, and other dimensions orgeometries are possible. In addition, while a feature of the presentinvention may have been described in the context of only one of theillustrated embodiments, such feature may be combined with one or moreother features of other embodiments, for any given application. It willalso be appreciated from the above that the fabrication of the uniquestructures herein and the operation thereof also constitute methods inaccordance with the present invention. The present invention alsoencompasses intermediate and end products resulting from the practice ofthe methods herein. The use of “comprising” or “including” alsocontemplates embodiments that “consist essentially of” or “consist of”the recited feature.

The explanations and illustrations presented herein are intended toacquaint others skilled in the art with the invention, its principles,and its practical application. Those skilled in the art may adapt andapply the invention in its numerous forms, as may be best suited to therequirements of a particular use. Accordingly, the specific embodimentsof the present invention as set forth are not intended as beingexhaustive or limiting of the invention. The scope of the inventionshould, therefore, be determined not with reference to the abovedescription, but should instead be determined with reference to theappended claims, along with the full scope of equivalents to which suchclaims are entitled. The disclosures of all articles and references,including patent applications and publications, are incorporated byreference for all purposes.

1. An endodontic composite sealant composition for filling and sealing a root canal comprising: cross-linked-polyisoprene microparticles.
 2. The composition of claim 1, wherein the cross-linked-polyisoprene microparticles are synthesized from cis-polyisoprene.
 3. The composition of claim 1, further comprising a polymerizable compound, a curing agent, and a filler.
 4. The composition of claim 3, wherein a portion of the polymerizable compound includes a ring-opening functionality, a reactive-cyclic functionality, a free radical functionality, or any combination thereof.
 5. The composition of claim 4, wherein the ring-opening functionality is selected from the group consisting of an acid group, an amine group, a thiol group and an alcohol group.
 6. The composition of claim 4, wherein the reactive-cyclic functionality is selected from the group consisting of an epoxy group, an anhydride group, an aziridine group and an oxazolone group.
 7. The composition of claim 4, wherein the free radical functionality is selected from the group consisting of a double bond and a triple bond.
 8. An endodontic composite sealant composition for filling and sealing a root canal comprising an adhesion promoter.
 9. The composition of claim 8, wherein a portion of the adhesion promoter includes a ring-opening functionality, a reactive-cyclic functionality, a free radical functionality, or any combination thereof.
 10. The composition of claim 8, wherein the adhesion promoter includes a dentin binding functionality.
 11. The composition of claim 10, wherein the dentin binding functionality includes a negative charge, a positive charge, an amphoteric charge, or a zwitterionic charge.
 12. The composition of claim 11, wherein the negative or positive charge comprises carboxylic acid groups, sulfate groups, amine groups, phosphate groups, quaternary ammonium groups and sulfonate, betaine, phosphatidylcholine groups.
 13. The composition of claim 1, wherein the cross-linked polyisoprene microparticles are less than about 200 um.
 14. The composition of claim 1, wherein the cross-linked-cis-polyisoprene microparticles range from about 50 to about 180 um.
 15. The composition of claim 1, wherein up to about 50% by weight is the cross-linked cis-polyisoprene powder, wherein the composition further comprises: up to about 80 weight % a radiopacifier selected from the group consisting of tungsten, zinc, zinc oxide, tungsten oxide, barium, barium sulfate, bismuth, bismuth oxide, and calcium tungstate; up to about 10% a curing agent, up to about 40% a filler, wherein the filler is a polymer, silica, cross-linked-cis-polyisoprene microparticles or fumed silica, or any combination thereof, and up to about 50% an adhesion promoter.
 16. A composition of claim 15, wherein the curing agent includes a catalyst having an amine group.
 17. The composition of claim 1, wherein the cross-linked-cis-polyisoprene microparticles comprises fibers, crosslinking agents, initiators, radiopacifiers, cis-polyisoprene, and/or antimicrobial agent.
 18. A composition of claim 17 wherein the initiator is selected from the group consisting of a free radical initiator or cationic initiator, and platinum initiator.
 19. The composition of claim 8, wherein adhesion promoter is characterized by the following formula (I): R¹—R²—W—Z—R³—R⁴   (I) wherein W is

or W is

and Z is

wherein R¹ and R⁴ are independently Hydrogen, NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; R² and R³ are independently a C₁₋₁₀ alkyl group, NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹³ group such that R¹³ is independently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, whereas multiple groups of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ may be identical or different; and x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and m is an integer from 1 to 1000, multiple groups of m may be identical or different.
 20. The composition of claim 19, wherein: i) R¹ and R⁴ are independently an epoxide, a succunic anhydride, or a succinimide group; ii) R¹ and R⁴ are independently NH₂, OH, COOH, or SH group; or iii) at least one of R¹ and R⁴ is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group.
 21. The composition of claim 19, wherein: i) R¹ and R⁴ are independently an epoxide, a succunic anhydride, or a succinimide group; and ii) at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently the C₁₋₁₀—R¹³ group such that R¹³ is independently the phosphate, the sulfate, the sulfonate, the betaine, the carboxylic acid, the amino acid, the diacids, the bisphosphate, or the phosphatidylcholine group.
 22. The composition of claim 19, wherein: i) R¹ and R⁴ are independently NH₂, OH, COOH, or SH group; and ii) at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently the C₁₋₁₀—R¹³ group such that R¹³ is independently the phosphate, the sulfate, the sulfonate, the betaine, the carboxylic acid, the amino acid, the diacids, the bisphosphate, or the phosphatidylcholine group.
 23. The composition of claim 19, wherein: i) at least one of R¹ and R⁴ is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; and ii) at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently the C₁₋₁₀—R¹³ group such that R¹³ is independently the NH₂, OH, COOH, SH, epoxide, succunic anhydride, or succinimide group, whereas NH₂, OH, COOH, or SH group is not present when the epoxide, the succunic anhydride, or the succinimide group is present.
 24. The composition of claim 19, wherein R⁵, R⁶, R¹¹, and R¹² are independently a C₁₋₁₀ alkyl group.
 25. The composition of claim 19, wherein W is

and wherein R¹ and R⁴ are independently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group; R² and R³ are independently a C₁₋₁₀ alkyl group; and R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹³ group such that R¹³ is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, whereas multiple groups of R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ may be identical or different.
 26. The composition according to claim 25, wherein NH₂, OH, COOH, or SH is not present when the epoxide, the succunic anhydride, or the succinimide group is present.
 27. The composition of claim 25, wherein at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² includes the C₁₋₁₀—R¹³ group.
 28. The composition of claim 25, wherein at least one of R⁷ and R⁸ includes the C₁₋₁₀—R¹³ group.
 29. The composition of claim 25, wherein R⁵, R⁶, R¹¹, and R¹² are independently a C₁₋₁₀ alkyl group
 30. The composition of claim 19, wherein W is

and wherein R¹ and R⁴ are independently Hydrogen, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, provided at least one of R¹ and R⁴ is not Hydrogen; R² and R³ are independently a C₁₋₁₀ alkyl group; and R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹³ group such that R¹³ is independently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group, whereas multiple groups of R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² may be identical or different, provided at least two of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² includes the C₁₋₁₀—R¹³ group.
 31. The composition according to claim 30, wherein NH₂, OH, COOH, or SH is not present when the epoxide, the succunic anhydride, or the succinimide group is present.
 32. The composition of claim 30, wherein at least two of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² includes the C₁₋₁₀—R¹³ group.
 33. The composition of claim 30, wherein x ranges from 1-50, y ranges from 25-250, and m is
 1. 34. The composition of claim 8, wherein the adhesion promoter includes a first component and a second component, a) the first component is characterized by the following formula (IIa): R¹—R²—W—Z—R³—R⁴   (IIa); wherein R¹ and R⁴ are independently NH₂, OH, COOH, or SH; R² and R³ are independently a C₁₋₁₀ alkyl group; W is

Z is

R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² are independently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹³ group such that R¹³ is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, whereas multiple groups of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ may be identical or different; x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and m is an integer from 1 to 10, multiple groups of m may be identical or different; and b) the second component is characterized by the following formula (IIb): R¹³—R¹⁴—W—Z—R¹⁵—R¹⁶   (IIb); wherein R¹³ and R¹⁶ are independently an epoxide, a succunic anhydride, or a succinimide group; R¹⁴ and R¹⁵ are independently a C₁₋₁₀ alkyl group; W is

Z is

R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², and R²³ are independently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R²⁴ group such that R²⁴ is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, whereas multiple groups of R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, and R²⁴ may be identical or different; q is an integer from 1 to 1000, multiple groups of q may be identical or different; r is an integer from 1 to 1000, multiple groups of r may be identical or different; and s is an integer from 1 to 10, multiple groups of s may be identical or different.
 35. The composition of claim 34, wherein i) at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² includes the C₁₋₁₀—R¹³ group; and/or ii) at least one of R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², and R²³ includes the C₁₋₁₀—R²⁴ group.
 36. The composition of claim 34, wherein i) at least one of R⁷ and R⁸ includes the C₁₋₁₀—R¹³ group; and/or ii) at least one of R¹⁸ and R¹⁹ includes the C₁₋₁₀—R²⁴ group.
 37. The composition of claim 34, wherein x ranges from 1-50, y ranges from 25-250, and m is 1 and wherein q ranges from 1-50, r ranges from 25-250, and s is
 1. 38. The composition of claim 8, wherein the adhesion promoter includes a first component and a second component, a) the first component is characterized by the following formula (IIIa): R¹—R²—W—Z—R³—R⁴   (IIIa); wherein R¹ and R⁴ are independently Hydrogen, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, provided at least one of R¹ and R⁴ is not Hydrogen; R² and R³ are independently a substituted or unsubstituted C₁₋₁₀ alkyl group; W is

Z is

R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² are independently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹³ group such that R¹³ is independently NH₂, OH, COOH, SH, whereas multiple groups of R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ may be identical or different; x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and m is an integer from 1 to 10, multiple groups of m may be identical or different; and b) the second component is characterized by the following formula (IIIb): R¹³—R¹⁴—W—Z—R¹⁵—R¹⁶   (IIIb); wherein R¹³ and R¹⁶ are independently Hydrogen, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, provided at least one of R¹ and R⁴ is not Hydrogen; R¹⁴ and R¹⁵ are independently a substituted or unsubstituted C₁₋₁₀ alkyl group; W is

Z is

R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², and R²³ are independently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R²⁴ group such that R²⁴ is independently an epoxide, a succunic anhydride, or a succinimide group, whereas multiple groups of R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, and R²⁴ may be identical or different; q is an integer from 1 to 1000, multiple groups of q may be identical or different; r is an integer from 1 to 1000, multiple groups of r may be identical or different; and s is an integer from 1 to 10, multiple groups of s may be identical or different.
 39. The composition of claim 38, wherein i) at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² includes the C₁₋₁₀—R¹³ group; and/or ii) at least one of R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², and R²³ includes the C₁₋₁₀—R²⁴ group.
 40. The composition of claim 38, wherein x ranges from 1-50, y ranges from 25-250, and m is 1; and wherein q ranges from 1-50, r ranges from 25-250, and s is
 1. 41. The composition of claim 8, wherein adhesion promoter is characterized by the following formula (IV): R¹—W—Z—R²   (IV) wherein R¹ and R² are independently a substituted or unsubstituted C₁₋₁₁ alkyl group; W is

or W is

and Z is

wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹¹ group such that R¹¹ is independently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; whereas multiple groups of R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ may be identical or different; provided that at least one of R³, R⁴ R⁵, R⁶, R⁷, and R⁸ includes the C₁₋₁₀—R¹¹ group; x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and m is an integer from 1 to 10, multiple groups of m may be identical or different.
 42. The composition according to claim 41, wherein NH₂, OH, COOH, or SH is not present when the epoxide, the succunic anhydride, or the succinimide group is present.
 43. The composition of claim 41, wherein W is

and wherein R³, R⁴, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ include the C₁₋₁₀ alkyl group; x ranges from 1-50; y ranges from 25-250; and m is
 1. 44. The composition of claim 8, wherein the adhesion promoter includes a first component and a second component, a) the first component is characterized by the following formula (IVa): R¹—W—Z—R²   (IVa) wherein R¹ and R² are independently a substituted or unsubstituted C₁₋₁₁ alkyl group; W is

and Z is

wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹¹ group such that R¹¹ is independently NH₂, OH, COOH, or SH; whereas multiple groups of R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ may be identical or different; provided that at least one of R³, R⁴ R⁵, R⁶, R⁷, and R⁸ includes the C₁₋₁₀—R¹¹ group; x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and m is an integer from 1 to 10, multiple groups of m may be identical or different; and b) the second component is characterized by the following formula (IVb): R¹²—W—Z—R¹³   (IVb) wherein R¹² and R¹³ are independently a substituted or unsubstituted C₁₋₁₁ alkyl group; W is

and Z is

wherein R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ are independently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R²² group such that R²² is independently an epoxide, a succunic anhydride, or a succinimide group; whereas multiple groups of R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, and R²² may be identical or different; provided that at least one of R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ includes the C₁₋₁₀—R¹¹ group; q is an integer from 1 to 1000, multiple groups of x may be identical or different; r is an integer from 1 to 1000, multiple groups of y may be identical or different; and s is an integer from 1 to 10, multiple groups of m may be identical or different.
 45. The composition of claim 44, wherein i) at least one of R⁵, R⁶, R⁷, and R⁸ includes the C₁₋₁₀—R¹¹ group; and ii) at least one of R¹⁶, R¹⁷, R¹⁸, and R¹⁹ includes the C₁₋₁₀—R²² group.
 46. The composition of claim 44, wherein x ranges from 1-50, y ranges from 25-250, and m is 1; and wherein q ranges from 1-50, r ranges from 25-250, and s is
 1. 47. The composition of claim 44, wherein i) at least one of R⁵, R⁶, R⁷, and R⁸ is independently a C₁₋₁₀—R²³ group such that R²³ is a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; whereas multiple groups of R⁵, R⁶, R⁷, and R⁸ may be identical or different; and/or ii) at least one of R¹⁶, R¹⁷, R¹⁸, and R¹⁹ is independently a C₁₋₁₀—R²⁴ group such that R²⁴ is a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; whereas multiple groups of R¹⁶, R¹⁷, R¹⁸, and R¹⁹ may be identical or different.
 48. The composition of claim 8, wherein the adhesion promoter is characterized by the following formula (V): R¹—R²—W—R³—R⁴   (V) wherein R¹ and R⁴ are independently Hydrogen, NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group; R² and R³ are independently a C₁₋₁₀₀₀ alkyl group; and W is

W is

or W is

wherein R⁵, R⁶, R⁷, R⁸, R⁹, R10 R¹¹, R¹², R¹³, R¹⁴, and R¹⁵, and R¹⁶ are independently Hydrogen, a C₁₋₁₀ alkyl group, or contain a linking group being linked to a NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, a phosphatidylcholine, a hydrocarbon, or a silicone, the linking group being selected from the group consisting of an acrylate group, a (meth)acrylate group, a siloxy acrylate group, a vinyl group, and an allyl group, whereas at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ contains the linking group and whereas multiple groups of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ may be identical or different; x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and z is an integer from 1 to 1000, multiple groups of z may be identical or different.
 49. The composition according to claim 48, wherein NH₂, OH, COOH, or SH is not present when the epoxide, the succunic anhydride, or the succinimide group is present.
 50. The composition of claim 48, wherein at least one of R¹ and R² is NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group.
 51. The composition of claim 48, wherein at least one of R¹³, R¹⁴, R¹⁵, and R¹⁶ contains the linking group being linked to a NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group.
 52. The composition of claim 48, wherein at least one of R⁵, R⁶, R⁷, R⁸ R⁹, R¹⁰, R¹¹, and R¹² contains the linking group being linked to a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, a phosphatidylcholine, a hydrocarbon, or a silicone.
 53. The composition of claim 48, wherein the silicone includes a Tris(trimethylsiloxy)silyl group.
 54. The composition according to claim 48, wherein W is

wherein R⁵, R⁶, R⁷, and R⁸ are independently a C₁₋₁₀ alkyl group or contain a linking group being linked to a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine, the linking group being selected from the group consisting of an acrylate group, a (meth)acrylate group, a siloxy acrylate group, a vinyl group, and an allyl group, whereas at least one of R⁵, R⁶, R⁷, and R⁸ contains the linking group and whereas multiple groups of R⁵, R⁶, R⁷, and R⁸ may be identical or different; R⁹, R¹⁰, R¹¹, and R¹² are independently a C₁₋₁₀ alkyl group or contain a linking group being linked to a hydrocarbon or a silicone group, the linking group being selected from the group consisting of an acrylate group, a (meth)acrylate group, a siloxy acrylate group, a vinyl group, and an allyl group, whereas at least one of R⁹, R¹⁰, and R¹² contains the linking group and whereas multiple groups of R⁹, R¹⁰ and R¹² may be identical or different; R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently a C₁₋₁₀ alkyl group or contain a linking group being linked to a NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group, the linking group being selected from the group consisting of an acrylate group, a (meth)acrylate group, a siloxy acrylate group, a vinyl group, and an allyl group, whereas at least one of R¹³, R¹⁴, R¹⁵, and R¹⁶ contains the linking group and whereas multiple groups of R¹³, R¹⁴, R¹⁵, and R¹⁶ may be identical or different; x is an integer from 1 to 100, multiple groups of x may be identical or different; y is an integer from 1 to 100, multiple groups of y may be identical or different; and z is an integer from 1 to 100, multiple groups of z may be identical or different.
 55. The composition according to claim 54, wherein NH₂, OH, COOH, or SH is not present when the epoxide, the succunic anhydride, or the succinimide group is present.
 56. The composition of claim 54, wherein the silicone includes a Tris(trimethylsiloxy)silyl group.
 57. The composition of claim 8, wherein the adhesion promoter includes a first component and a second component, a) the first component is characterized by the following formula (VIa): R¹—R²—W—R³—R⁴   (VIa); wherein R¹ and R⁴ are independently Hydrogen, an epoxide, a succunic anhydride, or a succinimide group; R² and R³ are independently a C₁₋₁₀₀₀ alkyl group; and W is

wherein R⁵, R⁶, R⁷, and R⁸ are independently Hydrogen, a C₁₋₁₀ alkyl group, or contain a linking group being linked to a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, a phosphatidylcholine, a hydrocarbon, or a silicone, the linking group being selected from the group consisting of an acrylate group, a (meth)acrylate group, a siloxy acrylate group, a vinyl group, and an allyl group, whereas at least one of R⁵, R⁶, R⁷, and R⁸ contains the linking group and whereas multiple groups of R⁵, R⁶, R⁷, and R⁸ may be identical or different; R⁹, R¹⁰, R¹¹, and R¹² are independently Hydrogen, a C₁₋₁₀ alkyl group, or contain a linking group being linked to a hydrocarbon or a silicone group, the linking group being selected from the group consisting of an acrylate group, a (meth)acrylate group, a siloxy acrylate group, a vinyl group, and an allyl group, whereas at [east one of R⁹, R¹⁰, R¹¹, and R¹² contains the linking group and whereas multiple groups of R⁹, R¹⁰, R¹¹, and R¹² may be identical or different; R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently Hydrogen, a C₁₋₁₀ alkyl group, or contain a linking group being linked to an epoxide, a succunic anhydride, or a succinimide group, the linking group being selected from the group consisting of an acrylate group, a (meth)acrylate group, a siloxy acrylate group, a vinyl group, and an allyl group, whereas at least one of R¹³, R¹⁴, R¹⁵, and R¹⁶ contains the linking group and whereas multiple groups of R¹³, R¹⁴, R¹⁵, and R¹⁶ may be identical or different; x is an integer from 1 to 1000, multiple groups x may be identical or different; and y is an integer from 1 to 1000, multiple groups y may be identical or different; and z is an integer from 1 to 1000, multiple groups z may be identical or different; and b) the second component is characterized by the following formula (VIb): R¹⁷—R¹⁸—W—R¹⁹—R²⁰   (VIb); wherein R¹⁷ and R²⁰ are independently Hydrogen, NH₂, OH, COOH, or SH; R¹⁸ and R¹⁹ are independently a C₁₋₁₀₀₀ alkyl group; and W is

wherein R²¹, R²², R²³, and R²⁴ are independently Hydrogen, a C₁₋₁₀ alkyl group, or contain a linking group being linked to a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, a phosphatidylcholine, a hydrocarbon, or a silicone, the linking group being selected from the group consisting of an acrylate group, a (meth)acrylate group, a siloxy acrylate group, a vinyl group, and an allyl group, whereas at least one of R²¹, R²², R²³, and R²⁴ contains the linking group and whereas multiple groups of R²¹, R²², R²³, and R²⁴ may be identical or different; R²⁵, R²⁶, R²⁷, and R²⁸ are independently Hydrogen, a C₁₋₁₀ alkyl group, or contain a linking group being linked to a hydrocarbon or a silicone group, the linking group being selected from the group consisting of an acrylate group, a (meth)acrylate group, a siloxy acrylate group, a vinyl group, and an allyl group, whereas at least one of R²⁵, R²⁶, R²⁷, and R²⁸ contains the linking group and whereas multiple groups of R²⁵, R²⁶, R²⁷, and R²⁸ may be identical or different; R²⁹, R³⁰, R³¹, and R³² are independently Hydrogen, a C₁₋₁₀ alkyl group, or contain a linking group being linked to a NH₂, OH, COOH, or SH group, the linking group being selected from the group consisting of an acrylate group, a (meth)acrylate group, a siloxy acrylate group, a vinyl group, and an allyl group, whereas at least one of R²⁹, R³⁰, R³¹, and R³² contains the linking group and whereas multiple groups of R²⁹, R³⁰, R³¹, and R³² may be identical or different; q is an integer from 1 to 1000, multiple groups of q may be identical or different; and r is an integer from 1 to 1000, multiple groups of r may be identical or different; and s is an integer from 1 to 1000, multiple groups of s may be identical or different.
 58. The composition according to claims 57, wherein the silicone of the first component, the second component, or both includes a Tris(trimethylsiloxy)silyl group.
 59. The composition according to claims 58, wherein the Tris(trimethylsiloxy)silyl group is [tris(trimethylsilyloxy)silyl]propyl methacrylate.
 60. A method for sealing a root canal with a composite sealant composition comprising the steps of: a. providing a mixture including cis-polyisoprene, a cross-linker, an initiator, a filler, zinc oxide and radiopacifier; b. curing the mixture to form a cured cross-linked cis-polyisoprene material; c. grinding the cured cross-linked cis-polyisoprene material cryogenically to form microparticles; d. providing a first component mixture including an epoxy based polymerizable compound and at least one of a radiopacifier, a filler, and the cured cross-linked cis-polyisoprene microparticles; e. providing a second component mixture including an amine-based polymerizable compound, a curing agent and at least one of a radiopacifier, a filler, and the cured cross-linked cis-polyisoprene microparticles; and f. filling the root canal with the first component mixture and the second component mixture to form a cured composite sealant material; g. wherein the first component mixture, the second component mixture, or both include the cured cross-linked cis-polyisoprene microparticles.
 61. The method according to claim 60, wherein the epoxy-based polymerizable compound is an epoxy modified polysiloxane compound.
 62. The method of claim 60, wherein the amine-based polymerizable compound is an amine modified polysiloxane compound.
 63. The method of claim 60, wherein the first component mixture, the second component mixture, or both include an adhesion promoter.
 64. The method of claim 63, wherein the adhesion promoter includes a silicon functionality.
 65. The method of claim 63, wherein the adhesion promoter includes a silicon functionality and an amine or epoxy functionality.
 66. The method of claim 60, wherein the first component mixture includes an adhesion promoter having a silicone functionality and an epoxy functionality.
 67. The method of claim 60, wherein the second component mixture includes an adhesion promoter having a silicone functionality and an amine functionality.
 68. The method of claim 60, wherein the first component mixture includes an adhesion promoter having a silicone functionality, an epoxy functionality, and a dentin binding functionality.
 69. The method of claim 60, wherein the second component mixture includes an adhesion promoter having a silicone functionality, an amine functionality, and a dentin binding functionality.
 70. The method of claim 60, wherein the dentin binding functionality is selected from the group consisting of a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, and a phosphatidylcholine.
 71. The method of claim 60, wherein the composite sealant material has a viscosity over 100,000 cps or putty-like.
 72. The method of claim 60, further comprising the step of inserting a gutta-percha point, an obturator, or a cross-linked gutta-percha-point into the root canal.
 73. The method of claim 60, wherein the gutta-percha point or carrier is surface modified.
 74. The method of claim 60, wherein the surface modification is corona treatment or plasma treatment.
 75. The method of claim 60, wherein the cross-linked cis-polyisoprene microparticles are not soluble in the composite sealant material.
 76. The method of claim 60, wherein the adhesion promoter is characterized by claim
 19. 77. The method of claim 60, wherein the adhesion promoter is characterized by claim
 25. 78. The method of claim 60, wherein the adhesion promoter is characterized by claim
 30. 79. The method of claim 60, wherein the adhesion promoter is characterized by claim
 34. 80. The method of claim 60, wherein the adhesion promoter is characterized by claim
 38. 81. The method of claim 60, wherein the adhesion promoter is characterized by claim
 41. 82. The method of claim 60, wherein the adhesion promoter is characterized by claim
 44. 83. The method of claim 60, wherein the adhesion promoter is characterized by claim
 48. 84. The method of claim 60, wherein the adhesion promoter is characterized by claim
 54. 85. The method of claim 60, wherein the adhesion promoter is characterized by claim
 57. 86. Use of the endodontic composite sealant composition of claim
 1. 87. An adhesion promoter comprising the following formula (I): R¹—R²—W—Z—R³—R⁴   (I) wherein W is

or W is

and Z is

wherein R¹ and R⁴ are independently Hydrogen, NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; R² and R³ are independently a C₁₋₁₀ alkyl group, NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently Hydrogen, a C₁₋₁₀ alkyl group, or a C₁₋₁₀—R¹³ group such that R¹³ is independently NH₂, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, whereas multiple groups of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ may be identical or different; and x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and m is an integer from 1 to 1000, multiple groups of m may be identical or different. 